Thermoplastic ink

ABSTRACT

A composition of matter useful for printing at elevated temperatures comprising polyethylene, an ester of rosin and minor amounts of coloring matter.

United States Patent Inventors Stanley P. Thompson;

Don L. Shoiner, both of Bartlesville, Okla.

Appl. No. 602,551

Filed Dec. 19, 1966 Patented Sept. 21, 1971 Assignee Phillips Petroleum Company THERMOPLASTIC [NK 2 Claims, No Drawings US. Cl 260/27, 111/36, 260/28.5, 260/897 Int. Cl C08f 29/02 Field of Search 260/27, 24,

Primary Examiner Donald E. Czaja Assistant Examiner-William B Parker Attorney-Young and Quigg ABSTRACT: A composition of matter useful for printing at elevated temperatures comprising polyethylene, an ester of rosin and minor amounts of coloring matter.

THERMOPLASTIC INK This invention relates to a composition of matter consisting of a thermoplastic ink. In another aspect, this invention relates to a method of printing using the particular composition of the invention.

Various printing operations are of substantial benefit in industrial operations. With respect to various articles of manufacture made from polyolefin, printing is a very significant vehicle for increasing their marketability and usefulness. A tremendous problem is encountered in that conventional inks fail to adhere to the untreated polyolefin surface.

This invention is superior over the prior art in that this invention provides an ink which is suitable for printing on polyolefin surfaces.

In one embodiment of this invention, a thermoplastic ink is compounded from a thermoplastic polymer of an olefin, an ester of rosin, and a pigment. In another embodiment, this novel composition is applied to a surface by a hot screen printing process.

Accordingly, it is an object of this invention to provide a novel composition of matter useful as a thermoplastic ink.

Another of this invention is to provide a method of printing using this novel composition of matter.

Other objects, advantages, and features of this invention will be readily apparent to those skilled in the art from the following description and appended claims.

According to this invention, a thermoplastic ink is compounded. The compositions of this invention comprise a base, consisting of a thermoplastic polymer of an olefin, compounded with a pigment, or coloring agent, and either a highly stabilized ester of rosin or a wax. In a preferred embodiment, the polymer comprises polyethylene.

The polymeric bases of the composition of this invention comprise polymers of olefins. Specifically, hydrocarbon polymers of an olefin containing less than four carbon atoms and possessing proper physical characteristics for use as an ink are satisfactory for the practice of this invention. In one embodiment, polyethylene, having a specific gravity of 0.927 and a melt index of 70, provided excellent results. According to this invention, the polymeric base can comprise about 40 to about 90 weight percent of the composition, when compounded with the ester of rosin, and can comprise about 70 to about 95 weight percent, when compounded with the wax. It is fully within the scope of this invention to add other polymeric materials to the base polymer.

The pigments, or coloring agents, of this invention can comprise any pigment or coloring agent capable of solution in the polymer in the desired proportion and possessing sufficient characteristics of durability and attractiveness as may be demanded by those practicing this invention. In the composition of this invention, the coloring agent can comprise any minor amountfSpecifically, the coloring agent of this invention can vary within the range of about 0.0001 to about weight percent of the composition.

The esters of rosin suitable for use in this invention comprise highly stabilized esters of rosin. In one embodiment, a highly stabilized pentaerythritol ester of rosin was entirely satisfactory. The amount of the ester of rosin in this invention is within the range of about 10 to about 60 weight percent of the composition. Additionally, it has been found that poor results are achieved when the ratio of the esters of rosin to the polymeric base are substantially higher than 1:1. Ratios substantially above 1:1 cause the ink to remain tacky and/or to become brittle upon cooling. If desired, wax can replace the ester of rosin in the compositions of this invention. In this invention, the wax can vary within the range of about 5 to about 30 weight percent of the composition.

The polymeric compositions of this invention have a viscosity before printing within the range of about 70 to about 250 Ml (ASTM 1238-62T). The polymers of this invention will remain in this viscosity range for at least 3 hours.

The polymeric compositions of this invention have a Sward Hardness within the range of about 3 to about 50 after said polymeric composition is place on the surface by printing and thereby transformed to its solid state.

According to this invention, a method of printing with the particular composition of the invention is provided. According to the method of this invention, the thermoplastic composition of the invention was applied to a polyethylene surface by use of a hot screen technique. The hot screen contains nonporous areas that prevent the ink from going through said screen and porous areas that allow the ink to go through said screen. The porous area then represents the design or letter to be printed. Specifically, this hot screen technique involves placing the ink upon the porous area of a screen, said screen being capable of withstanding temperatures above the melting point of the thermoplastic ink. According to this invention, the screen temperature must be controlled at a temperature that will melt the polymer and produce proper viscosity but not chemically change it. Specifically, a screen temperature range of 275 F. to 350 F. was satisfactory with the polyethylene base previously described. Departure from these temperature ranges by operating below 275 F. will cause the screen to plug" and thereby terminate the printing operation. Departure from these ranges by operating above 350 F. will cause a chemical change in the polymers rendering the polymers unusable as an ink base. The remaining porous area of the screen, containing the design or characters to be printed, then is capable of permitting the thennoplastic ink to pass therethrough onto the surface to which the screen is in contact. According to this invention, the surface to which the ink is to be applied is maintained, and held for a sufficient time for good printing results, at a level substantially below that of the melting point of the thermoplastic ink and, as a consequence, the ink solidifies immediately upon contact with the surface. Mechanical means can be used to aid the thermoplastic ink in flowing through the porous portion of the screen. Such mechanical means can comprise an means capable of forcing ink through the porous area and not interfering with other steps in the printing operation. Rollers, squeegees, and the like, are entirely satisfactory for the practice of this invention. According to this invention, only a very thin or, printing film" is left on the surface to be printed. The printed surface is the removed from the screen and another blank surface to be printed is placed in contact with the screen and the cycle is repeated.

The ink must remain at a temperature above that of its melting point for the duration of the printing operation in order to possess sufficient viscosity characteristics to flow properly through the porous portions of the screen. An additional consideration is that at increased temperature cross-linking of the polymer chains is likely to occur. As a result, it is possible to operate at higher temperatures when a coarser screen is used because the increased cross-linking is less likely to cause plugging of the screen. The compositions of this invention can be maintained within the range of about 200 F. to about 400 F. when the screen size is 180 mesh or finer. When the screen size is coarser than 180 mesh, a temperature within the range of about 200 F. to about 450 F. can be used. As explained above, higher operating temperatures are possible with a coarser screen because there is less likelihood of plugging the screen. In one embodiment, .a 180 mesh screen printed well at 275 F. with the polyethylene base previously described.

The temperature range must, however, be maintained with the above recited ranges in order that the viscosity of the ink be maintained in the range of about 70 to about 250 Ml (ASTM 1238-62T). Viscosities above 250 Ml produce poor printing because the ink flows too freely. Viscosities below 70 Ml also produce poor quality printing as the ink is not sufficiently thin to flow through the porous portion of the screen.

According to this invention, the polymeric compositions of this invention possess a pot life of at least 3 hours. That is, they will demonstrate no substantial viscosity change within 3 hours after assuming a liquid state. The printing operation, therefore, enjoys the advantage that the printing operation can consume any period of time up to 3 hours.

As has been previously recited, the thermoplastic ink of this composition will possess a Sward Hardness within the range of of an approximate 1:1 ratio of polymer and base is demonstrated. Runs 3, 4 and 7 indicate a composition consisting of polyethylene, pigment, and wax. These runs indicate that ranges of about to about 20 percent wax produces a good print, but as much as about 40 percent renders the formulation unsatisfactory. These runs also indicate the necessity of the wax, together with the polyethylene, for good printing results. Run 8 indicates a comp'osition of consisting of polyethylene and pigment. This is unsatisfactory in that the composition becomes rubbery and unworkable after minutes. The necessity of the ester or wax is thereby demonstrated.

TABLE I Percent Pentae- Ethylene rythritol polymer ester of Run No base rosin Pigment Wax Remarks 49 49 2 Very good results.

50 50 Very good results through 180 mesh screen at 275 F.

88 2 10 Good adhesion, fair print.

78 2 Good adhesion, slightly harder than Run 3.

78 20 2 Good adhesion, fair print with 180 mesh screen at 300 F.-10 good prints-second best formulation.

47 47 6 Good adhesion, printed at 275 F. with 180 mesh screen-excellent prints, continuous printing could be madebest formulation.

58 2 40 Poor quality prints-no adhesion.

98 2 Poor resultsbecame rubbery after 15 minutes at operating temperature.

are satisfactory while others are not. Runs 1, 5 and 6 indicate a formulation consisting of polyethylene base, pentaerythritol ester of rosin and pigment. This formulation works well in ranges of about 1 part polyethylene to about 1 part ester of rosin (runs 1 and 6) and the range can be as high as about 80 percent polyethylene and about 20 percent ester of rosin (run 5) for satisfactory results. Run 2 indicates only an ethylene and ester of rosin formulation with no pigment. This run shows that the existence of pigment is not essential for a successful formulation. A successful formulation depends than on ingredients other than the pigment. Additionally, theoperability We claim:

1. A composition of matter useful for printing at elevated temperatures comprising polyethylene in the range of about to about 40 weight percent of the total composition, an ester of rosin in the range of about 10 to about 60 weight percent of the total composition, and minor amounts of a coloring agent.

2. The composition of claim 1 wherein the viscosity is within the range of about 70 to about 250 Ml (ASTM 1238-62T) for at least 3 hours, wherein the Sward Hardness is within the range of about 3 to about 50 in its solid state. 

2. The composition of claim 1 wherein the viscosity is within the range of about 70 to about 250 MI (ASTM 1238-62T) for at least 3 hours, wherein the Sward Hardness is within the range of about 3 to about 50 in its solid state. 